Dihalogen Indolocarbazole Monomers and Poly(Indolocarbazoles)

ABSTRACT

Monomers and polymers based on dihalogen indolocarbazole and poly(indolocarbazoles), and methods of making such and using the same are described, as well as organic electronic devices incorporating the same.

CROSS REFERENCE

This application claims benefit to U.S. Provisional Application Ser. No.60/640,482, filed Dec. 30, 2004, and 60/694,916, filed Jun. 28, 2005,the disclosures of which are both incorporated herein by reference intheir entireties.

FIELD

This disclosure relates generally to dihalogen indolocarbazole monomersand polymers and poly(indolocarbazoles), for example, those found inorganic electronic devices, and materials and methods for fabrication ofthe same.

BACKGROUND

Organic electronic devices convert electrical energy into radiation,detect signals through electronic processes, convert radiation intoelectrical energy, or include one or more organic semiconductor layers.Charge transport materials facilitate migration of positive or negativecharges through the organic device with relative efficiency and smallloss of charges.

Thus, charge transport materials are important for the fabrication oforganic electronic devices, and their development is a goal in theindustry.

SUMMARY

Provided are dihalogen indolocarbazole monomers having a Formula I orII:

wherein R₁-R₄ are, independently at each occurrence, alkyl, heteroalkylaromatic, or heteroaromatic groups, and u and v are independently 1, 2,or 3. The monomer is selected from a cis isomer (Formula II) or a transisomer (Formula I). Polymers made therefrom, organic electronic devicesor articles of manufacture incorporating, and methods of making the sameare also provided.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 shows a synthesis route for a dihalogen indolocarbazole,specifically, dichloroindolocarbazole, by a three-step reaction.

FIG. 2 shows the method known as Yamamoto Polymerization for preparationof indolocarbazole-based polymers, wherein A is the function group andcan be selected from bromo, chloro, and iodo group.

FIG. 3 shows the reaction scheme for synthesis of1,4-Bis(2′-nitro-4′-chlorophenyl)benzene.

FIG. 4 shows the reaction scheme for synthesis of3,9-Dichloro-5,11-dihydromdolo[3,2-b]carbazole

FIG. 5 shows the reaction scheme for synthesis ofN,N′-Di(2′-ethylhexyl)-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole.

FIG. 6 shows the reaction scheme for synthesis ofN,N′-Di(2′-ethylhexyl)-3,8-dichloro-5,6-dihydromdolo[1,2-b]carbazole.

FIG. 7 shows the reaction scheme for synthesis ofN,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole.

FIG. 8 shows the reaction scheme for synthesis ofpoly(N,N′-Di(2′-ethylhexyl)-5,11-dihydroindolo[3,2-b]carbazole).

FIG. 9 shows the reaction scheme for synthesis of poly{N,N′-bis[20[2-[2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole}.

FIG. 10 shows the reaction scheme for synthesis of poly{N,N′-bis[20[2-[2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-phenylene).

FIG. 11 shows the reaction scheme for synthesis ofpoly{N,N′-bis[2-[2-[2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-9,9-bis[2-[2-[2-methoxyethoxy)ethoxy]ethyl]-fluorene}.

FIG. 12 shows the reaction scheme for synthesis of poly{9,9-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]fluorene}.

FIG. 13 shows the reaction scheme for synthesis of poly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}.

FIG. 14 shows electrochemistry of poly(N,N-diethylhexylindolocarbazole).

FIG. 15 shows the electrochemistry ofpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d]bisoxazole}.

FIG. 16 shows the photoluminescence (PL) spectra ofpoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}, individually and blended.

FIG. 17 shows the photoluminescence (PL) spectra of a blend ofpoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole},and the blend that has been doped with a green emitter.

FIG. 18 shows the EL spectra of a blend ofpoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole} for blue LED.

FIG. 19 shows the EL spectra of a blend ofpoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole},and the blend that has been doped with 0.5% by weight perylenedicarboxylic acid diiobutyl ester for green LED.

FIG. 20 is a schematic diagram of an organic electronic device.

The figures are provided by way of example and are not intended to limitthe invention. Skilled artisans appreciate that objects in the figuresare illustrated for simplicity and clarity and have not necessarily beendrawn to scale. For example, the dimensions of some of the objects inthe figures may be exaggerated relative to other objects to help toimprove understanding of embodiments.

DETAILED DESCRIPTION

Monomers and polymers based on dihalogen indolocarbazole andpoly(indolocarbazoles) are disclosed. In one embodiment, the polymersoffer high molecular weight and/or good solubility and/or a fullyconjugated main chain. In another embodiment, the polymers offer chargetransport characteristics, for example, hole transport; and are neutral.In an embodiment, the polymers can be used in organic electronicdevices, such as organic light-emitting diodes (OLEDs), for use incharge transport layers.

Provided are dihalogen indolocarbazole monomers having a structureaccording to Formula I or II

wherein R₁-R₄ are, independently at each occurrence, alkyl, heteroalkylaromatic, or heteroaromatic groups, and u and v are, independently, 1,2, or 3.

In one embodiment, one or more nonadjacent methyl or methylene groupscan be replaced by —O—, —S—, —NR′—, or an aromatic or heteroaromaticring.

In some embodiments, the monomers include1,4-Bis(2′-nitro-4′-chlorophenyl)benzene;3,9-Dichloro-5,11-dihydromdolo[3,2-b]carbazole;N,N′-Di(2′-ethylhexyl)-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole;N,N′-Di(2′-ethylhexyl)-3,8-dichloro-5,6-dihydromdolo[1,2-b]carbazole;N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole;or derivatives thereof.

A method of making dihaloindolocarbazole monomers, in one embodiment,comprises reacting a first aromatic compound comprising R₃ and R₄ and asecond aromatic compound comprising R₂ and a halogen with a firstcatalyst to form a first intermediate aromatic compound comprising R₂,R₃ and R₄; mixing a second catalyst with the first intermediate compoundto form a second intermediate aromatic compound comprising R₂, R₃ andR₄; and mixing the second intermediate aromatic compound with R₁ to forma dihalogen indolocarbazole monomer; wherein: R₁-R₄ are, independentlyat each occurrence, alkyl, heteroalkyl aromatic, or heteroaromaticgroups, and u and v are, independently, 1, 2, or 3. One detailedembodiment of making a dichioroindolocarbazole, by a three-stepreaction, is depicted in FIG. 1.

In the methods of making the monomers of the disclosure, the firstcatalyst mixture comprises, for example, CH₃CN, PPh₃, (PPh₃)₄Pd, K₂CO₃,KOH, THF, 2-ethylhexylbromide,2-[2-(2-methoxyethoxy)ethoxy]ethylbromide, toluene, or combinationsthereof. In one example, the second catalyst mixture comprises P(OEt)₃.

In one embodiment, the above-described monomers are used to makeoligamers.

In one embodiment, the above-described monomers are used to form apolymer. In some embodiments, the polymers includePoly(N,N′-Di(2′-ethylhexyl)-5,11-dihydroindolo[3,2-b]carbazole);Poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole};Poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-phenylene};Poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-9,9-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-fluorene}; Poly{9,9-bis [2-[2-(2-methoxyethoxy)ethoxy]ethyl]fluorene};poly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole},wherein n is greater than 20; combinations thereof, conjugates thereof,or derivatives thereof.

In one embodiment, the polymers are used to make co-polymers. In anotherexample, the polymers comprise block copolymers. In still anotherembodiment, the monomers are used to make homopolymers.

In some embodiments, the polymers are used to form a layer in an organicelectronic device.

The general structures of charge transport polymers based onindolocarbazole are:

wherein R₁-R₄ are, independently at each occurrence, alkyl, heteroalkylaromatic groups, or heteroaromatic groups and u and v are the number ofsubstituents on the benzene ring and are, independently, 1, 2, or 3. Inone embodiment, one or more nonadjacent methyl or methylene groups canbe replaced by —O—, —S—, —NR′—, or an aromatic or heteroaromatic ring.

FIG. 2 shows the method known as Yamamoto Polymerization for preparationof indolocarbazole-based charge transport polymers, wherein A is thefunction group and can be selected from bromo, chloro, and iodo group.In one embodiment, a polymer has at least 5 repeating units. Derivativesand conjugates of indolocarbazole polymers may also be desirable for usein charge transport layers, such as hole transport layers.

To make a hole transport polymer, conjugate, or derivative thereof basedon indolocarbazole in different applications, solubility control is aconsideration. When poly(indolocarbazole) is used in the blend withanother charge transport material, solubility of both materials shouldbe compatible to avoid phase separation.Similar-solubility-control-side-chains are chosen for bothpoly(indolocarbazole) and charge transport material.

For example, whenpoly{bis[9,9-di(2′-ethylhexyl)fluoren-2-yl]-benzo[1,2-d:4,5-d′]bisoxazole}:

is selected as a charge transport material, for example, an electrontransport material, a similar side chain, e.g., from the ethlyhexylgroup, is selected for poly(indolocarbazole) so that both materials canbe easily soluble in the same solvent such as toluene.

When a multiple layer device structure is used, the desiredpoly(indolocarbazole) should have different solubility as the electrontransport material to prevent solvent erosion from solution of electrontransport material coated on the top of it. For example, when toluenesolublepoly{bis[9,9-di(2′-ethylhexyl)fluoren-2-yl]-benzo[1,2-d:4,5-d′]bisoxazole}is chosen as an electron transport material, the selection of the sidechain of poly(indolocarbazole) should make it insoluble in toluene. Weuse more polar side chain such as 2-[2-(2-methoxyethoxy)ethoxy]ethylgroup as a side chain for poly(indolocarbazole) to make it soluble inchlorinated solvent such as tetrachloroethane, while insoluble intoluene.

Compositions comprising dihalogen indolocarbazole monomers, dihalogenindolocarbazole-based polymers, or combinations thereof include asolvent, a processing aid, or combinations thereof. These compositionscan be in any form, including, but not limited to solvents, emulsions,and colloidal dispersions.

The compositions can further comprise a charge transporting material, acharge blocking material, or combinations thereof. In some embodiments,the monomers are used to form a hole transport material. Hole transport,hole injection, and electron-withdrawing are used synonymously in thisdisclosure, and refer to a material that facilitates migration ofpositive charges through the material with relative efficiency and smallloss of charge.

In some embodiments, the polymers are used to form a layer in an organicelectronic device.

Organic electronic devices comprising dihalogen indolocarbazole monomersor derivatives thereof; or dihalogen indolocarbazole-based polymers, orconjugates thereof, or derivatives thereof are also provided. In someembodiments, the monomer or the polymer forms a buffer layer, preferablythe buffer layer is a hole transport layer. Devices include, but are notlimited to light-emitting diodes, light-emitting diode displays, diodelasers, photodetectors, photoconductive cells, photoresistors,photoswitches, phototransistors, phototubes, IR-detectors, photovoltaicdevices, solar cells, light sensors, photoconductors,electrophotographic devices, and organic transistors.

In one embodiment, compositions are provided comprising theabove-described compounds and at least one solvent, processing aid,charge transporting material, or charge blocking material. Thesecompositions can be in any form, including, but not limited to solvents,emulsions, and colloidal dispersions.

Device

Referring to FIG. 20, an exemplary organic electronic device 100 isshown. The device 100 includes a substrate 105. The substrate 105 may berigid or flexible, for example, glass, ceramic, metal, or plastic. Whenvoltage is applied, emitted light is visible through the substrate 105.

A first electrical contact layer 110 is deposited on the substrate 105.For illustrative purposes, the layer 110 is an anode layer. Anode layersmay be deposited as lines. The anode can be made of, for example,materials containing or comprising metal, mixed metals, alloy, metaloxides or mixed-metal oxide. The anode may comprise a conductingpolymer, polymer blend or polymer mixtures. Suitable metals include theGroup 11 metals, the metals in Groups 4, 5, and 6, and the Group 8, 10transition metals. If the anode is to be light-transmitting, mixed-metaloxides of Groups 12, 13 and 14 metals, such as indium-tin-oxide, aregenerally used. The anode may also comprise an organic material,especially a conducting polymer such as polyaniline, including exemplarymaterials as described in Flexible Light-Emitting Diodes Made FromSoluble Conducting Polymer, Nature 1992, 357, 477-479. At least one ofthe anode and cathode should be at least partially transparent to allowthe generated light to be observed.

An optional buffer layer 120, such as hole transport materials, may bedeposited over the anode layer 110, the latter being sometimes referredto as the “hole-injecting contact layer.” Examples of hole transportmaterials suitable for use as the layer 120 have been summarized, forexample, in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 18,837-860 (4^(th) ed. 1996). Both hole transporting “small” molecules aswell as oligomers and polymers may be used. Hole transporting moleculesinclude, but are not limited to:N,N′diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD), 1,1bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N′bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD), tetrakis(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA),a-phenyl 4-N,N-diphenylaminostyrene (TPS), p (diethylamino)benzaldehydediphenylhydrazone (DEH), triphenylamine (TPA), bis[4(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP), 1phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP), 1,2 trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB),N,N,N′,N′tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB),and porphyrinic compounds, such as copper phthalocyanine. Useful holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, and polyaniline.Conducting polymers are useful as a class. It is also possible to obtainhole transporting polymers by doping hole transporting moieties, such asthose mentioned above, into polymers such as polystyrenes andpolycarbonates.

An organic layer 130 may be deposited over the buffer layer 120 whenpresent, or over the first electrical contact layer 110. In someembodiments, the organic layer 130 may be a number of discrete layerscomprising a variety of components. Depending upon the application ofthe device, the organic layer 130 can be a light-emitting layer that isactivated by an applied voltage (such as in a light-emitting diode orlight-emitting electrochemical cell), or a layer of material thatresponds to radiant energy and generates a signal with or without anapplied bias voltage (such as in a photodetector).

Other layers in the device can be made of any materials which are knownto be useful in such layers upon consideration of the function to beserved by such layers.

Any organic electroluminescent (“EL”) material can be used as aphotoactive material (e.g., in layer 130). Such materials include, butare not limited to, fluorescent dyes, small molecule organic fluorescentcompounds, fluorescent and phosphorescent metal complexes, conjugatedpolymers, and mixtures thereof. Examples of fluorescent dyes include,but are not limited to, pyrene, perylene, rubrene, derivatives thereof,and mixtures thereof. Examples of metal complexes include, but are notlimited to, metal chelated oxinoid compounds, such astris(8-hydroxyquinolato)aluminum (Alq3); cyclometalated iridium andplatinum electroluminescent compounds, such as complexes of Iridium withphenylpyridine, phenylquinoline, or phenylpyrimidine ligands asdisclosed in Petrov et al., Published PCT Application WO 02/02714, andorganometallic complexes described in, for example, publishedapplications US 2001/0019782, EP 1191612, WO 02/15645, and EP 1191614;and mixtures thereof. Electroluminescent emissive layers comprising acharge carrying host material and a metal complex have been described byThompson et al., in U.S. Pat. No. 6,303,238, and by Burrows and Thompsonin published PCT applications WO 00/70655 and WO 01/41512. Examples ofconjugated polymers include, but are not limited topoly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes),polythiophenes, poly(p-phenylenes), copolymers thereof, and mixturesthereof.

In one embodiment of the devices of the invention, photoactive materialcan be an organometallic complex. In another embodiment, the photoactivematerial is a cyclometalated complex of iridium or platinum. Otheruseful photoactive materials may be employed as well. Complexes ofiridium with phenylpyridine, phenylquinoline, or phenylpyrimidineligands have been disclosed as electroluminescent compounds in Petrov etal., Published PCT Application WO 02/02714. Other organometalliccomplexes have been described in, for example, published applications US2001/0019782, EP 1191612, WO 02/15645, and EP 1191614.Electroluminescent devices with an active layer of polyvinyl carbazole(PVK) doped with metallic complexes of iridium have been described byBurrows and Thompson in published PCT applications WO 00/70655 and WO01/41512. Electroluminescent emissive layers comprising a chargecarrying host material and a phosphorescent platinum complex have beendescribed by Thompson et al., in U.S. Pat. No. 6,303,238, Bradley etal., in Synth. Met. 2001, 116 (1-3), 379-383, and Campbell et al., inPhys. Rev. B, Vol. 65 085210.

A second electrical contact layer 160 is deposited on the organic layer130. For illustrative purposes, the layer 160 is a cathode layer.

Cathode layers may be deposited as lines or as a film. The cathode canbe any metal or nonmetal having a lower work function than the anode.Exemplary materials for the cathode can include alkali metals,especially lithium, the Group 2 (alkaline earth) metals, the Group 12metals, including the rare earth elements and lanthanides, and theactinides. Materials such as aluminum, indium, calcium, barium, samariumand magnesium, as well as combinations, can be used. Lithium-containingand other compounds, such as LiF and Li₂O, may also be deposited betweenan organic layer and the cathode layer to lower the operating voltage ofthe system.

An electron transport layer 140 or electron injection layer 150 isoptionally disposed adjacent to the cathode, the cathode being sometimesreferred to as the “electron-injecting contact layer.”

An encapsulation layer 170 is deposited over the contact layer 160 toprevent entry of undesirable components, such as water and oxygen, intothe device 100. Such components can have a deleterious effect on theorganic layer 130. In one embodiment, the encapsulation layer 170 is abarrier layer or film.

Though not depicted, it is understood that the device 100 may compriseadditional layers. For example, there can be a layer (not shown) betweenthe anode 110 and hole transport layer 120 to facilitate positive chargetransport and/or band-gap matching of the layers, or to function as aprotective layer. Other layers that are known in the art or otherwisemay be used. In addition, any of the above-described layers may comprisetwo or more sub-layers or may form a laminar structure. Alternatively,some or all of anode layer 110 the hole transport layer 120, theelectron transport layers 140 and 150, cathode layer 160, and otherlayers may be treated, especially surface treated, to increase chargecarrier transport efficiency or other physical properties of thedevices. The choice of materials for each of the component layers ispreferably determined by balancing the goals of providing a device withhigh device efficiency with device operational lifetime considerations,fabrication time and complexity factors and other considerationsappreciated by persons skilled in the art. It will be appreciated thatdetermining optimal components, component configurations, andcompositional identities would be routine to those of ordinary skill ofin the art.

In one embodiment, the different layers have the following range ofthicknesses: anode 110, 500-5000 Å, in one embodiment 1000-2000Å; holetransport layer 120, 50-2000 Å, in one embodiment 200-1000 Å;photoactive layer 130, 10-2000 Å, in one embodiment 100-1000 Å; layers140 and 150, 50-2000 Å, in one embodiment 100-1000 Å; cathode 160,200-10000 Å, in one embodiment 300-5000 Å. The location of theelectron-hole recombination zone in the device, and thus the emissionspectrum of the device, can be affected by the relative thickness ofeach layer. Thus the thickness of the electron-transport layer should bechosen so that the electron-hole recombination zone is in thelight-emitting layer. The desired ratio of layer thicknesses will dependon the exact nature of the materials used.

In operation, a voltage from an appropriate power supply (not depicted)is applied to the device 100. Current therefore passes across the layersof the device 100. Electrons enter the organic polymer layer, releasingphotons. In some OLEDs, called active matrix OLED displays, individualdeposits of photoactive organic films may be independently excited bythe passage of current, leading to individual pixels of light emission.In some OLEDs, called passive matrix OLED displays, deposits ofphotoactive organic films may be excited by rows and columns ofelectrical contact layers.

Devices can be prepared employing a variety of techniques. Theseinclude, by way of non-limiting exemplification, vapor depositiontechniques and liquid deposition. Devices may also be sub-assembled intoseparate articles of manufacture that can then be combined to form thedevice.

Note that not all of the activities described above in the generaldescription are required, that a portion of a specific activity may notbe required, and that one or more further activities may be performed inaddition to those described. Still further, the order in whichactivities are listed are not necessarily the order in which they areperformed.

Definitions

The term “monomer” refers to a compound capable of being polymerized.The term “monomeric unit” refers to units which are repeated in apolymer.

The term “polymer” is intended to mean a material having at least onerepeating monomeric unit. The term includes homopolymers having only onekind of monomeric unit, and copolymers having two or more differentmonomeric units. Copolymers are a subset of polymers.

The term “group” is intended to mean a part of a compound, such as asubstituent in an organic compound or a ligand in a metal complex. Theprefix “hetero” indicates that one or more carbon atoms have beenreplaced with a different atom. The term “alkyl” is intended to mean agroup derived from an aliphatic hydrocarbon having one point ofattachment.

As used herein, the term “alkyl” refers to a monovalent straight orbranched chain hydrocarbon group having from one to about 100 carbonatoms, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, n-hexyl, and the like.

As used herein, “heteroaryl” refers to aromatic rings containing one ormore heteroatoms (e.g., N, O, S, or the like) as part of the ringstructure, and having in the range of 5 up to 14 carbon atoms and“substituted heteroaryl” refers to heteroaryl groups further bearing oneor more substituents as set forth above.

Aryl is any type of substituted or unsubstituted aromatic group; a and bare a statistical percentage of indolocarbazole unit and aryl group. Theterm “aryl” is intended to mean a group derived from an aromatichydrocarbon having one point of attachment, and aryl can be one or acombination of several different aromatic groups; n is the number of therepeating units and can be from 3-1000.

The phrase “adjacent to,” when used to refer to layers in a device, doesnot necessarily mean that one layer is immediately next to anotherlayer. On the other hand, the phrase “adjacent R groups,” is used torefer to R groups that are next to each other in a chemical formula(i.e., R groups that are on atoms which are joined by a bond).

The use of “a” or “an” are employed to describe elements and componentsof the invention. This is done merely for convenience and to give ageneral sense of the invention. This description should be read toinclude one or at least one and the singular also includes the pluralunless it is obvious that it is meant otherwise.

The term “active” when referring to a layer or material is intended tomean a layer or material that exhibits electronic or electro-radiativeproperties. An active layer material may emit radiation or exhibit achange in concentration of electron-hole pairs when receiving radiation.Thus, the term “active material” refers to a material whichelectronically facilitates the operation of the device. Examples ofactive materials include, but are not limited to, materials whichconduct, inject, transport, or block a charge, where the charge can beeither an electron or a hole. Examples of inactive materials include,but are not limited to, planarization materials, insulating materials,and environmental barrier materials.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

The term “layer” is used interchangeably with the term “film” and refersto a coating covering a desired area. The area can be as large as anentire device or a specific functional area such as the actual visualdisplay, or as small as a single sub-pixel. Films can be formed by anyconventional deposition technique, including vapor deposition and liquiddeposition. Liquid deposition techniques include, but are not limitedto, continuous deposition techniques such as spin coating, gravurecoating, curtain coating, dip coating, slot-die coating, spray-coating,and continuous nozzle coating; and discontinuous deposition techniquessuch as ink jet printing, gravure printing, and screen printing.

The term “organic electronic device” is intended to mean a deviceincluding one or more semiconductor layers or materials. Organicelectronic devices include, but are not limited to: (1) devices thatconvert electrical energy into radiation (e.g., a light-emitting diode,light emitting diode display, diode laser, or lighting panel), (2)devices that detect signals through electronic processes (e.g.,photodetectors photoconductive cells, photoresistors, photoswitches,phototransistors, phototubes, infrared (“IR”) detectors, or biosensors),(3) devices that convert radiation into electrical energy (e.g., aphotovoltaic device or solar cell), and (4) devices that include one ormore electronic components that include one or more organicsemiconductor layers (e.g., a transistor or diode). The term device alsoincludes coating materials for memory storage devices, antistatic films,biosensors, electrochromic devices, solid electrolyte capacitors, energystorage devices such as a rechargeable battery, and electromagneticshielding applications.

The term “substrate” is intended to mean a workpiece that can be eitherrigid or flexible and may include one or more layers of one or morematerials, which can include, but are not limited to, glass, polymer,metal, or ceramic materials, or combinations thereof.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will Control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in _(t)extbooks and other sources within the organiclight-emitting diode display, photodetector, photovoltaic, andsemiconductive member arts.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1 Preparation of 1,4-Bis(2′-nitro-4′-chlorophenyl)benzene

FIG. 3 shows the reaction scheme for synthesis of1,4-Bis(2′-nitro-4′-chlorophenyl)benzene.

A one liter flask charged with l-bromo-4-chloro-2-nitrobenzene (91.76 g,388.0 mmol), 1,4-phenylenebisboronic acid (32.16 g, 194.0 mmol),potassium carbonate (55.28 g, 400.0 mmol), benzyltriethylammoniumchloride (1000 mg, 4.4 mmol), PPh₃ (1.20 g, 4.56 mmol), and Pd(PPh₃)₄(1.20 g, 1.08 mmol) was flushed with nitrogen. Acetonitrile (300 mL) andwater (150 mL) was then added.

After stirring at room temperature (RT) under nitrogen for 5 minutes,the mixture was heated to and maintained at reflux (oil bath temp 90°C.) for 68 hours. The mixture was allowed to cool to room temperatureand poured into 10% HCl solution (400 mL) then filtered off theprecipitate. The precipitate was washed with water (150 mL) and allowedto air dry. The dry powder was rinsed with cool THF and dried again toafford 39.25 g (52%)of the desired product.

¹H NMR (500 MHz, DMF-d₇) δ ppm: 8.24 (d, J=2.0 Hz, 2H), 7.94 (dd, J=8.3,2.0 Hz, 2H), 7.57 (s, 4H), 7.73 (d, J=8.3 Hz, 2H).

Example 2 Preparation of 3,9-Dichloro-5,11-dihydromdolo[3,2-b]carbazole

FIG. 4 shows the reaction scheme for synthesis of3,9-Dichloro-5,11-dihydromdolo[3,2-b]carbazole.

A 500-mL flask charged with 1,4-bis(2′-nitro-4′-chlorophenyl)benzene(36.97 g, 95.0 mmol) was flushed with argon. Triethylphosphite (150 mL)was then added. After stirring at room temperature (RT) under argon for5 minutes, the mixture was heated to and maintained at oil bath temp153° C. for 21 hours. The mixture was allowed to cool to roomtemperature and poured into a mixture of ethanol (500 mL) and water (50mL). The precipitate was collected, washed with ethanol (50 mL) anddried to give the cis[1,2-b] product (4.66 g, 15%) as a pale yellowishpowder. Then water (300 mL) was added to the filtrate. The precipitatewas collected, and washed with cool ethanol (50 mL) and dried to givethe trans[3,2-b] product (25.49 g, 82.5%) as a brownish powder.

Trans[3,2-b] isomer:

¹H NMR (500 MHz, THF-d₈) δ 7.19 (dd, J=8.3, 1.5 Hz, 2H), 7.55 (d, J=1.34Hz, 2H), 7.88 (s, 2H), 8.06 (d, J=8.3 Hz, 2H), 10.28 (s, 2H).

Cis[1,2-b] isomer:

¹H NMR (500 MHz, THF-d₈) δ 7.10 (dd, J=8.3,1.44 Hz, 2H), 7.40 (d, J=1.44Hz, 2H), 8.02 (s, 2H), 8.06 (d, J=8.3 Hz, 2H), 10.30 (s, 2H).

Example 3 Preparation ofN,N′-Di(2′-ethylhexyl)-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole

FIG. 5 shows the reaction scheme for synthesis ofN,N′-Di(2′-ethylhexyl)-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole.

A 250-mL flask charged with3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole (9.76 g, 30.0 mmol) andpotassium hydroxide (16.84 g, 300.0 mmol) was flushed with nitrogen. THF(100 mL) was then added. The mixture was heated to and maintained at 80°C. (oil bath temp) for 2 hours. 2-Ethylhexylbromide (23.17 g, 120.0mmol) was added to the reaction mixture and maintained at the sameconditions (80° C.) for 20 hours. The mixture was allowed to cool toroom temperature and poured into water (150 mL), and then extracted withhexanes (3×150 mL). The combined organic layer was washed with water(2×150 mL), brine (150 mL), and then dried over magnesium sulfate. Thecrude product was purified by column chromatography using hexanes aseluent on silica gel to afford the desired product.

¹H NMR (500 MHz, GDC13) δ ppm: 8.00 (d, J=8.25 Hz, 2H), 7.87 (s, 2H),7.49 (d, J=1.70 Hz, 2H), 7.44 (dd, J=8.25,1.70 Hz, 2H), 4.49 (d, J=7.63Hz, 4H), 1.89 (m, 2H), 0.61-1.05 (m, 16H), 0.50-0.61 (m, 12H),

¹³C NMR (125 MHz, CDC13) δ ppm: 143.54, 130.83, 130.52, 124.50, 123.78,120.95, 120.67, 113.41, 112.10, 52.13, 38.27, 29.73, 27.68, 23.38,22.84, 13.87, 10.29.

Example 4 Preparation ofN,N′-Di(2′-ethylhexyl)-3,8-dichloro-5,6-dihydromdolo[1,2-b]carbazole

FIG. 6 shows the reaction scheme for synthesis ofN,N′-Di(2′-ethylhexyl)-3,8-dichloro-5,6-dihydromdolo[1,2-b]carbazole.

A 50-mL flask charged with3,8-dichloro-5,6-dihydroindolo[1,2-b]carbazole (1.95 g, 6.0 mmol) andpotassium hydroxide (4.04 g, 72 mmol) was flushed with nitrogen. THF (20mL) was then added. The mixture was heated to and maintained at 80° C.(oil bath temperature) for 2 hours. 2-Ethylhexylbromide (6.95 g, 26mmol) was added to the reaction mixture and maintained at the sameconditions (80° C.) for 17 hours.

The mixture was allowed to cool to room temperature and poured intowater (50 mL), and then extracted with hexanes (3×50 mL). The combinedorganic layer was washed with water (2×50 mL), brine (50 mL), and thendried over magnesium sulfate.

The crude product was purified by column chromatography using hexanes asan eluent on silica gel to afford the desired product.

¹H NMR (500 MHz, CDC13) δ ppm: 8.04 (d, J=8.20 Hz, 2H), 7.84 (s, 2H),7.33 (d, J=1.38 Hz, 2H), 7.17 (dd, J=8.20,1.38 Hz, 2H), 4.13 (m, 4H),2.12 (m, 2H), 1.10-1.50 (m, 16H), 0.75-1.00 (m, 12H).

Example 5 Preparation ofN,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole

FIG. 7 shows the reaction scheme for synthesis ofN,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-3,9-dichloro-5,11-dihydroindolo[3,2-b]carbazole.

Example 6 General Procedure of Polymerization through the YomamotoReaction

FIG. 2 shows the method known as Yamamoto Polymerization forindolocarbazole-based charge transport material, wherein A is thefunction group and can be selected from bromo, chloro, and iodo group.

A Schlenck flask equipped with a stirring bar was charged withbis(1,5-cyclooctadiene)-nickel(O) (2.02 equiv.), 2,2′-bipyridyl (2.02equiv.), 1,5-cyclooctadiene (2.02 equiv.) and DMF (¼ of toluene volume).The mixture was stirred under an argon atmosphere at 65° C. for 30minutes and then the temperature was increased to 70° C. A solution ofthe monomer(s) (1.00 equiv.) in toluene ([monomer]=⅙ M) was added to themixture, which was then allowed to stir for 16 to 115 hours.Bromobenzene was added and the reaction mixture was allowed to stir for1 hour. After the mixture was allowed to cool to room temperature,concentrated hydrochloric acid was added and the reaction mixture wasallowed to stir for a further 5 minutes. The whole mixture was pouredslowly into methanol to precipitate the polymer. The polymer/methanolmixture was then filtered. The polymer isolated by filtration was thenfurther re-precipitated into methanol from chloroform solution. Thepolymer was now taken up again in chloroform for washing with KOH (10 wt% aqueous), EDTA (aqueous, pH 7.0), and de-ionized water. The organiclayer was passed through a 5 μm filter and precipitated into methanol.The collected solid was dried under reduced pressure at 45° C.overnight.

Example 6a Poly(N,N′-Di(2′-ethylhexyl)-5,11-dihydroindolo[3,2-b]carbazole)

FIG. 8 shows the reaction scheme for synthesis of poly(N,N′-Di(2′-ethylhexyl)-5,11-dihydroindolo[3,2-b]carbazole). Theresulting material was a light yellow solid, having a yield of 75%.

Example 6b Poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole}

FIG. 9 shows the reaction scheme for synthesis ofpoly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole}.The resulting material was a light yellow solid, having a yield of 49%.

Example 6cPoly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-phenylene)(50/50 mole %)

FIG. 10 shows the reaction scheme for synthesis of poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-phenylene}.The resulting material was a light yellow solid, having a yield of 62%.

Example 6d Poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-9,9-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-fluorene) (50/50 mole %)

FIG. 11 shows the reaction scheme for synthesis of poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-9,9-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]- fluorene}. The resulting materialwas a light yellow solid, having a yield of 84%.

Example 6e Poly{9,9-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]fluorene}

FIG. 12 shows the reaction scheme for synthesis of poly{9,9-bis[2-[2-[2-methoxyethoxy)ethoxy]ethyl]fluorene}. The resulting materialwas a light yellow solid, having a yield of 88%.

Example 6fPoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}

Electron transport material prepared in accordance with FIG. 13. Theresulting material was a light yellow solid, having a yield of 87%.

Example 7 Electrochemistry of poly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}

FIG. 14 shows that electrochemistry ofpoly(N,N-diethylhexylindolocarbazole). The energy levels of HOMO andLUMO were estimated to be 5.4 and 2.2 eV, respectively. FIG. 15 showsthe electrochemistry ofpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}.The energy levels of HOMO and LUMO were estimated to be 5.8 and 2.8 eV,respectively.

This example demonstrates that a blend of thepoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}can be used for as a charge transport material, e.g., a hole transportmaterial. The HOMO energy level of poly(N,N-diethylhexylindolocarbazole)determined by electrochemistry showed that it is easier to be oxidized,i.e. easier hole injection.

This example also demonstrates thatpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}can be used as an electron transport material. The LUMO energy level ofpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}determinedby electrochemistry showed it is easier to be reduced, i.e. easierelectron injection.

Example 8 PL Spectra of poly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole},and PL Spectrum of Blend for Blue LED

FIG. 16 shows the PL spectra of poly(N,N-diethylhexylindolocarbazole)andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole},and the PL spectrum of blend for a blue LED. This example demonstratesthat poly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}can be blended without causing any photoluminescence quench. Thephotoluminescence of the blend is mainly from the emission ofpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]benzo[1,2-d;4,5-d′]bisoxazole}.

Example 9 PL Spectra of Blend of poly(N,N-diethylhexylindolocarbazole),poly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]benzo[1,2-d;4,5-d′]bisoxazole)& perylene dicarboxylic acid diisobutyl ester for Green LED

FIG. 17 shows the PL spectra of blend ofpoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole} & the blend containing perylene dicarboxylic aciddiisobutyl ester for green LED. This example demonstrates that a greenemissive layer can be formulated bypoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}blend doped with a low concentration of green emitter.

Example 10 EL Device Fabrication ofpoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}Blend for Blue LED

FIG. 18 shows the EL spectrum for apoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}blend. This example demonstrates a blue LED can be fabricated by thisblend. The low operating voltage of the device confirmed the balancecarrier injection.

ITO/PEDT/Blend of HT (poly(N,N-diethylhexylindolocarbazole)) and ET(poly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole})/LiF/AlC.I.E. Coordinate: u′=0.143, v′=0.328 Device performance: 200 cd/m23.7V0.6 cd/A

Example 11 EL Device Fabrication ofpoly(N,N-diethylhexylindolocarbazole) andpoly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}Blend and Perylene Dicarboxylic Acid Diisobutyl Ester Dopant for Green

FIG. 19 shows the EL spectrum for a poly(N,N-dithylhexylindolocarbazole)andpoly(2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole}blend, and the blend doped with 0.5% by weight perylene dicarboxylicacid diisobutyl ester dopant.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges include each and everyvalue within that range.

1-20. (canceled)
 21. A compound made from a monomer of formula I or IIcomprising an oligamer or a polymer

wherein: R₁ is hydrogen, 2′-ethylhexyl, or2-[2-(2-methoxyethoxy)ethoxy]ethyl, provided that when the monomer is ofFormula I, R₁ is 2′-ethylhexyl, or 2-[2-(2-methoxyethoxy)ethoxy]ethyl.22. A polymer of claim 21 comprising a co-polymer, a homopolymer, ablock co-polymer, or combinations thereof.
 23. The polymer of claim 22that is poly(N,N-Di(2′-ethylhexyl)-5,11-dihydroindolo[3,2-b]carbazole);poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole};poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-phenylene};poly{N,N′-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-5,11-dihydroindolo[3,2-b]carbazole-co-9,9-bis[2-[2-(2-methoxyethoxy)ethoxy]ethyl]-fluorene}; poly{9,9-bis [2-[2-(2-methoxyethoxy)ethoxy]ethyl]fluorene};poly{2-[9,9-Bis-(2-ethyl-hexyl)-7-methyl-9H-fluoren-2-yl]-6-[9-(2-ethyl-butyl)-9-(2-ethyl-heptyl)-7-methyl-9H-fluoren-2-yl]-benzo[1,2-d;4,5-d′]bisoxazole},wherein n is greater than 20; combinations thereof, conjugates thereof,or derivatives thereof.
 24. A material comprising an oligomer or apolymer of claim
 21. 25. The material of claim 24 further comprising asolvent, a processing aid, or combinations thereof.
 26. An organicelectronic device having at least one layer comprising the material ofclaim
 24. 27. The device of claim 26 wherein the material forms a chargetransport layer.
 28. The device of claim 26 wherein the charge transportlayer is a hole transport layer.
 29. The device of claim 26 that is alight-emitting diode, a light-emitting diode display, a diode laser, aphotodetector, a photoconductive cell, a photoresistor, a photo switch,a phototransistor, a phototube, an IR-detector, a photovoltaic device, asolar cell, a light sensor, a photoconductor, an electrophotographicdevice, or an organic transistor.